CN107978743B - Sodium-ion battery positive electrode material, preparation method thereof and sodium-ion battery - Google Patents
Sodium-ion battery positive electrode material, preparation method thereof and sodium-ion battery Download PDFInfo
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Abstract
The invention discloses a sodium-ion battery anode material, wherein the molecular formula of the sodium-ion battery anode material is Na4Fe0.5Mn0.5V(PO4)3It is a trigonal system, the space group is R-3c, and it is an irregular sheet structure. The invention also discloses a preparation method of the sodium-ion battery anode material, which comprises the steps of dissolving a sodium source, an iron source, a manganese source, a vanadium source and a phosphorus source in deionized water according to a stoichiometric ratio, adding a mixed solution of tetraethylene glycol and ethylene glycol, and stirring at room temperature for reaction to obtain a mixed solution; transferring the mixed solution into a reaction kettle, heating for reaction to obtain viscous colloid, and freeze-drying the viscous colloid to obtain precursor powder; and calcining the precursor powder at high temperature in an inert atmosphere to obtain the sheet-shaped sodium-ion battery anode material. The method has the advantages of good repeatability, simple operation and industrial application prospect, and the invention also provides a sodium ion battery using the sodium ion battery anode material, and the sodium ion battery has excellent electrochemical performance.
Description
Technical Field
The invention belongs to the technical field of sodium ion batteries, and particularly relates to a sodium ion battery positive electrode material, a preparation method thereof and a sodium ion battery.
Background
The lithium ion battery has high specific capacity and high energy density, so that the lithium ion battery is widely applied to portable electronic equipment and popularization and application of the ion battery in the field of large energy storage systems. Sodium ion batteries have become hot research at home and abroad as effective substitutes for lithium ion batteries. Sodium has similar physicochemical properties with lithium, and the sodium resource has considerable storage in the earth crust (the earth crust abundance of lithium is 0.006%, and the earth crust abundance of sodium is 2.64%), so that the sodium-ion battery has great advantages in cost, and the sodium-ion battery is the most potential battery system for large-scale energy storage commercial application.
In order to meet the requirements of practical application, high voltage and high energy density are the development directions of the positive electrode material of the sodium-ion battery. Compared with an oxide system and a Prussian blue analogue system, the polyanion type sodium-ion battery positive electrode material shows higher voltage due to the induction effect of polyanion. The polyanion material has an open ion diffusion channel, and has high structural stability and thermal stability, thereby having great application prospect. Among polyanionic systems, the fast ion conductor type (NASICON) material, again sodium, is of greatest interest. Sodium vanadium phosphate (Na) is added to the NASICON type positive electrode material3V2(PO4)3) The development of positive electrode materials of sodium-ion batteries is greatly promoted by the most attention of the positive electrode materials of the sodium-ion batteries due to the excellent high rate and the excellent cycling stability of the positive electrode materials. But Na3V2(PO4)3The conductivity is low, and the voltage plateau is 3.4V and still needs to be improved.
Patent document CN201710364045 discloses a vanadium manganese sodium phosphate @3D porous graphene composite material, a preparation method thereof and an application thereof in a sodium ion battery. The flaky vanadium manganese sodium phosphate grows on the 3D porous graphene framework in situ, and the advantages of large specific surface area and large contact surface with electrolyte of the flaky vanadium manganese sodium phosphate are combined with the advantages of stable loose three-dimensional pore channel structure, large specific surface area, good load stability and the like of the 3D porous graphene, so that the problem of low conductivity of the vanadium manganese sodium phosphate material is effectively solved, and the performance of the material is improved.
Disclosure of Invention
In view of the above-mentioned shortcomings and drawbacks of the prior art, an object of the present invention is to provide a positive electrode material for sodium-ion batteries, which has low cost and good electrochemical performance.
The invention also aims to provide a preparation method of the sodium-ion battery cathode material, which is simple to operate and has industrial application prospect.
Another object of the present invention is to provide a sodium ion battery using the above positive electrode material, which has good specific discharge capacity, good rate capability and cycle performance.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
the molecular formula of the positive electrode material of the sodium-ion battery is Na4Fe0.5Mn0.5V(PO4)3Is a trigonal system, is an R-3c space group, and has a sheet structure.
Preferably, the specific surface area of the positive electrode material of the sodium-ion battery is 3-100 m2/g。
The vanadium-manganese-iron-sodium phosphate cathode material disclosed by the invention has the advantages that part of vanadium in the vanadium-sodium phosphate is replaced by iron and manganese, wherein the conductivity of the cathode material is improved by adding the iron, and the voltage of the cathode material is improved by adding the manganese. The molecular formula of the vanadium manganese iron sodium phosphate anode material is Na4Fe0.5Mn0.5V(PO4)3The positive electrode material formed by each element at the specific ratio is a trigonal system, the space group is R-3c, the appearance is an irregular flaky structure, the purity is high, and the phase is uniform (each element forms more impurity phases at other ratios, and cannot form a uniform phase with high purity). The special crystal structure enables the vanadium manganese iron sodium phosphate anode material to have a multidimensional sodium ion diffusion channel, and is more beneficial to the rapid migration of sodium ions compared with anode materials with other structures, thereby being beneficial to improving the electrochemical performance of the anode material and a sodium ion battery prepared from the anode material. And moreover, the irregular sheet structure is also beneficial to improving the electron/ion diffusion dynamics of the material and improving the electrochemical performance of the material. Compared with the composite material of patent document CN201710364045, the vanadium manganese iron sodium phosphate cathode material with the special structure of the invention omits the use of expensive graphene, and adopts iron to partially replace vanadium (the price of iron is lower than that of vanadium), so that the performance of the vanadium manganese iron sodium phosphate cathode material is improved, and the production cost of the material is effectively reduced.
The invention also provides a preparation method of the sodium-ion battery positive electrode material, which comprises the following steps:
(1) dissolving a sodium source, an iron source, a manganese source, a vanadium source and a phosphorus source in deionized water according to a stoichiometric ratio to ensure that the concentration of vanadium ions in the solution is 0.05-0.1 mol/L, then adding a mixed solution of tetraethylene glycol and ethylene glycol, and stirring at room temperature to obtain a mixed solution, wherein the volume ratio of the tetraethylene glycol to the ethylene glycol in the mixed solution of the tetraethylene glycol and the ethylene glycol is 1 (0.5-2);
(2) transferring the mixed solution obtained in the step (1) into a reaction kettle, reacting for 8-12 h at 160-200 ℃ to obtain viscous colloid, and then freeze-drying the viscous colloid to obtain precursor powder;
(3) and (3) calcining the precursor powder obtained in the step (2) for 6-12 hours at the temperature of 650-850 ℃ in an inert atmosphere to obtain the positive electrode material of the sodium-ion battery.
The preparation method comprises the steps of dissolving a sodium source, an iron source, a manganese source, a vanadium source and a phosphorus source in deionized water at a specific ratio, adding a mixed solution of tetraethylene glycol and ethylene glycol to form a hydrothermal reaction system containing tetraethylene glycol and ethylene glycol, and controlling the volume ratio of tetraethylene glycol and ethylene glycol, the concentration of vanadium ions in the solution system, the temperature and time of the hydrothermal reaction and the temperature and time of calcination to obtain Na with a specific structure (trigonal system, R-3c space group and irregular sheet)4Fe0.5Mn0.5V(PO4)3A positive electrode material of a sodium ion battery. The preparation method is the Na with the special structure of the invention4Fe0.5Mn0.5V(PO4)3The anode material is corresponding, and the cooperation between the preparation method and the product structure is realized.
Preferably, in the step (1), the ratio of the volume of the mixed solution of the tetraethylene glycol and the ethylene glycol to the volume of the deionized water is 1: (1.5-3.5).
Preferably, in the step (1), the stirring time at room temperature is 0.5-1.5 h. Further preferably 1 hour.
Preferably, in the step (2), the temperature of the reaction is preferably 180 ℃.
Preferably, in the step (1), the sodium source is one or more of sodium acetate, sodium carbonate, sodium bicarbonate, sodium dihydrogen phosphate and disodium hydrogen phosphate.
Preferably, in the step (1), the iron source is one or more of ferrous oxalate, ferrous acetate, ferric citrate and ferric ammonium citrate.
Preferably, in the step (1), the manganese source is one or more of manganese acetate, manganese oxalate and manganese nitrate.
Preferably, in the step (1), the vanadium source is one or more of metavanadate, vanadium acetylacetonate, vanadyl acetylacetonate, and sodium orthovanadate.
Preferably, in the step (1), the phosphorus source is one or more of phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate, disodium hydrogen phosphate and sodium dihydrogen phosphate.
Preferably, in the step (3), the inert atmosphere is one or more of argon, nitrogen and a mixed gas of hydrogen and argon.
The invention also provides a sodium ion battery, wherein the sodium ion battery positive electrode material or the sodium ion battery positive electrode material prepared by the preparation method is used, and the electrochemical performance of the sodium ion battery is tested. For example, the irregular flakes of Na4Fe0.5Mn0.5V(PO4)3The material is mixed with a conductive agent and a binder, and then coated on an aluminum foil to prepare the positive electrode of the sodium-ion battery. The conductive agent and the binder used may be those known to those skilled in the art. The method for assembling and preparing the positive electrode material of the sodium-ion battery can also refer to the existing method. For example, the irregular flaky Na prepared by the present invention4Fe0.5Mn0.5V(PO4)3Grinding the materials, conductive carbon black and PVDF binder according to the mass ratio of 8:1:1, fully mixing, adding NMP to form uniform slurry, and coating the uniform slurry on aluminum foilFor testing electrode, metal sodium is used as counter electrode, and its electrolyte is 1M NaClO 4100% PC, preparing a sodium half cell and testing the electrochemical performance of the sodium half cell.
Compared with the prior art, the invention has the advantages that:
(1) the positive electrode material of the sodium-ion battery is a trigonal system, is an R-3c space group and has a molecular formula of Na4Fe0.5Mn0.5V(PO4)3The anode material has high purity and uniform phase, has a multidimensional sodium ion diffusion channel, is beneficial to the rapid migration of sodium ions, and has excellent electrochemical performance.
(2) The sodium-ion battery positive electrode material provided by the invention has the advantages that iron is adopted to partially replace vanadium, and compared with the existing composite positive electrode material of vanadium-manganese-sodium phosphate and graphene, the sodium-ion battery positive electrode material provided by the invention has the advantages that the material performance is improved, and meanwhile, the production cost of the material is effectively reduced.
(3) The vanadium manganese iron sodium phosphate in the sodium ion battery anode material has an irregular sheet structure and a large specific surface area, so that the electron/ion diffusion kinetics of the material are improved, and the electrochemical performance of the material is further improved.
(4) In the preparation method of the sodium-ion battery cathode material, a mixed solution of tetraethylene glycol and ethylene glycol is added into a solution of a sodium source, an iron source, a manganese source, a vanadium source and a phosphorus source (a hydrothermal reaction system containing tetraethylene glycol and ethylene glycol is formed), and the volume ratio of tetraethylene glycol and ethylene glycol, the concentration of vanadium ions in the solution system, the temperature and time of the hydrothermal reaction and the temperature and time of calcination are controlled to obtain Na with a specific structure4Fe0.5Mn0.5V(PO4)3The positive electrode material of the sodium-ion battery realizes the synergy of the preparation method and the product structure.
(5) The preparation method of the sodium-ion battery cathode material has the advantages of good repeatability, simple operation and industrial application prospect.
(6) The sodium ion battery assembled by the positive electrode material of the sodium ion battery has high specific discharge capacity, good rate performance and cycle performance, the capacity of the sodium ion battery reaches over 73mAh/g under 5C rate, the specific discharge capacity of the sodium ion battery reaches 89mAh/g after 50 cycles under 2C rate, and the capacity retention rate of the sodium ion battery reaches 89%.
In summary, the invention combines a special preparation method under a specific element proportion to obtain a crystal system with trigonal crystal system, R-3c space group and a molecular formula of Na4Fe0.5Mn0.5V(PO4)3The sodium ion battery cathode material with high purity and uniform phase effectively reduces the production cost and improves the performance of the sodium ion battery cathode material and the sodium ion battery prepared from the material.
Drawings
FIG. 1 shows Na obtained in example 1 of the present invention4Fe0.5Mn0.5V(PO4)3Scanning Electron Micrographs (SEM) of the sodium ion battery positive electrode material.
FIG. 2 shows Na obtained in example 1 of the present invention4Fe0.5Mn0.5V(PO4)3XRD of the positive electrode material of the sodium-ion battery.
FIG. 3 shows Na obtained in example 1 of the present invention4Fe0.5Mn0.5V(PO4)3And the rate performance diagram of the sodium-ion battery assembled by the positive electrode material of the sodium-ion battery.
FIG. 4 shows Na obtained in example 1 of the present invention4Fe0.5Mn0.5V(PO4)3And (3) a cycle performance diagram of the sodium-ion battery assembled by the positive electrode material of the sodium-ion battery under the 2C multiplying power.
Detailed Description
In order to facilitate an understanding of the invention, the invention will be described more fully and in detail below with reference to the accompanying drawings and preferred embodiments, but the scope of the invention is not limited to the specific embodiments below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Example 1:
dissolving 0.04mol of sodium acetate, 0.005mol of ferrous oxalate, 0.005mol of manganese acetate, 0.01mol of ammonium metavanadate and 0.03mol of ammonium dihydrogen phosphate in 150m L of deionized water, adding 60m of mixed solution of L of tetraethylene glycol and ethylene glycol (volume ratio is 1: 1), stirring at room temperature for 1h to obtain mixed solution, transferring the obtained mixed solution into a reaction kettle, reacting at 180 ℃ for 10h to obtain viscous colloid, freeze-drying the viscous colloid to obtain precursor powder, calcining the precursor powder at 750 ℃ for 8h in argon atmosphere to obtain Na4Fe0.5Mn0.5V(PO4)3A positive electrode material of a sodium ion battery.
Prepared Na4Fe0.5Mn0.5V(PO4)3The morphology (SEM) of the positive electrode material is shown in fig. 1, which is seen from fig. 1, which is an irregular sheet structure. FIG. 2 shows Na obtained4Fe0.5Mn0.5V(PO4)3XRD pattern of the positive electrode material, as can be seen from FIG. 2, the obtained material was confirmed to be Na4Fe0.5Mn0.5V(PO4)3The target product has less impure phase, uniform phase and high purity; the Na is obtained by theoretical fitting4Fe0.5Mn0.5V(PO4)3The anode material is a trigonal system, and the space group is R-3 c. The sodium ion battery positive electrode material prepared in this example and a sodium sheet were assembled into a button cell, and the rate performance of the button cell was tested, and the test results are shown in fig. 3. As can be seen from FIG. 3, Na obtained in this example was used4Fe0.5Mn0.5V(PO4)3The sodium ion battery prepared from the cathode material has excellent rate performance, and the capacity of 83.1mAh/g is still achieved even under the rate of 5C. Fig. 3 is a graph of the cycling performance of the button cell at 2C rate. As can be seen from FIG. 4, after 50 cycles under the 2C multiplying power, the discharge specific capacity reaches 89.8mAh/g, and the capacity retention rate reaches 89%. The Na obtained in this example was tested by BET4Fe0.5Mn0.5V(PO4)3The specific surface area of the positive electrode material of the sodium-ion battery is 58.2m2/g。
Example 2:
taking 0.04mol of sodium acetate, 0.005mol of ferrous oxalate, 0.005mol of manganese acetate, 0.01mol of ammonium metavanadate and 0.03mol of ammonium dihydrogen phosphate into 100m L of deionized water, adding 60m of mixed solution of L of tetraethylene glycol and glycol (volume ratio is 1: 1), stirring for 1h at room temperature to obtain mixed solution, transferring the obtained mixed solution into a reaction kettle, reacting for 10h at 180 ℃ to obtain viscous colloid, freeze-drying the viscous colloid to obtain precursor powder, calcining the precursor powder for 8h at 750 ℃ under argon atmosphere to obtain Na with an irregular sheet structure4Fe0.5Mn0.5V(PO4)3A positive electrode material of a sodium ion battery. It is a trigonal system with a space group of R-3c and a uniform phase.
Na prepared in this example4Fe0.5Mn0.5V(PO4)3The button cell is assembled by the positive electrode material of the sodium-ion battery and the sodium sheet, and the test shows that the button cell has the specific discharge capacity of 78.1mAh/g under the multiplying power of 5C. BET test shows that the Na4Fe0.5Mn0.5V(PO4)3The specific surface area of the positive electrode material of the sodium-ion battery is 57.6m2/g。
Example 3:
taking 0.04mol of sodium acetate, 0.005mol of ferrous oxalate, 0.005mol of manganese acetate, 0.01mol of ammonium metavanadate and 0.03mol of ammonium dihydrogen phosphate into 200m L of deionized water, adding 60m of mixed solution of L of tetraethylene glycol and glycol (volume ratio is 1: 1), stirring for 1h at room temperature to obtain mixed solution, transferring the obtained mixed solution into a reaction kettle, reacting for 10h at 180 ℃ to obtain viscous colloid, freeze-drying the viscous colloid to obtain precursor powder, calcining the precursor powder for 8h at 750 ℃ under argon atmosphere to obtain Na with an irregular sheet structure4Fe0.5Mn0.5V(PO4)3A positive electrode material of a sodium ion battery. It is a trigonal system with a space group of R-3c and a uniform phase.
Preparation Using this exampleNa of (2)4Fe0.5Mn0.5V(PO4)3The button cell is assembled by the positive electrode material of the sodium-ion battery and the sodium sheet, and the test shows that the button cell has the specific discharge capacity of 81.2mAh/g under the multiplying power of 5C.
Example 4:
taking 0.04mol of sodium acetate, 0.005mol of ferrous oxalate, 0.005mol of manganese acetate, 0.01mol of ammonium metavanadate and 0.03mol of ammonium dihydrogen phosphate into 150m L of deionized water, adding 60m of mixed solution of L of tetraethylene glycol and glycol (volume ratio is 1: 0.5), stirring for 1h at room temperature to obtain mixed solution, transferring the obtained mixed solution into a reaction kettle, reacting for 10h at 180 ℃ to obtain viscous colloid, freeze-drying the viscous colloid to obtain precursor powder, calcining the precursor powder for 8h at 750 ℃ under argon atmosphere to obtain Na with irregular sheet structure4Fe0.5Mn0.5V(PO4)3A positive electrode material of a sodium ion battery. It is a trigonal system with a space group of R-3c and a uniform phase.
Na prepared in this example4Fe0.5Mn0.5V(PO4)3The button cell is assembled by the positive electrode material of the sodium-ion battery and the sodium sheet, and the test shows that the button cell has the specific discharge capacity of 76.4mAh/g under the multiplying power of 5C.
Example 5:
taking 0.04mol of sodium acetate, 0.005mol of ferrous oxalate, 0.005mol of manganese acetate, 0.01mol of metavanadate and 0.03mol of ammonium dihydrogen phosphate into 150m L of deionized water, adding 60m of mixed solution of L of tetraethylene glycol and glycol (volume ratio is 1: 2), stirring for 1h at room temperature to obtain mixed solution, transferring the obtained mixed solution into a reaction kettle, reacting for 10h at 180 ℃ to obtain viscous colloid, freeze-drying the viscous colloid to obtain precursor powder, calcining the precursor powder for 8h at 750 ℃ under argon atmosphere to obtain Na with irregular sheet structure4Fe0.5Mn0.5V(PO4)3A positive electrode material of a sodium ion battery. It is a trigonal system with a space group of R-3c and a uniform phase.
Na prepared in this example4Fe0.5Mn0.5V(PO4)3The button cell is assembled by the positive electrode material of the sodium-ion battery and the sodium sheet, and the test shows that the button cell has the specific discharge capacity of 73.7mAh/g under the multiplying power of 5C.
Example 6:
taking 0.04mol of sodium acetate, 0.005mol of ferrous oxalate, 0.005mol of manganese acetate, 0.01mol of ammonium metavanadate and 0.03mol of ammonium dihydrogen phosphate into 150m L of deionized water, adding 60m of mixed solution of L of tetraethylene glycol and glycol (volume ratio is 1: 1), stirring for 1h at room temperature to obtain mixed solution, transferring the obtained mixed solution into a reaction kettle, reacting for 8h at 180 ℃ to obtain viscous colloid, freeze-drying the viscous colloid to obtain precursor powder, calcining the precursor powder for 8h at 850 ℃ under argon atmosphere to obtain Na with an irregular sheet structure4Fe0.5Mn0.5V(PO4)3A positive electrode material of a sodium ion battery. It is a trigonal system with a space group of R-3c and a uniform phase.
Na prepared in this example4Fe0.5Mn0.5V(PO4)3The button cell is assembled by the positive electrode material of the sodium-ion battery and the sodium sheet, and the test shows that the button cell has the specific discharge capacity of 80.4mAh/g under the multiplying power of 5C.
Example 7:
taking 0.04mol of sodium acetate, 0.005mol of ferrous oxalate, 0.005mol of manganese acetate, 0.01mol of ammonium metavanadate and 0.03mol of ammonium dihydrogen phosphate into 150m L of deionized water, adding 60m of mixed solution of L of tetraethylene glycol and glycol (volume ratio is 1: 1), stirring for 1h at room temperature to obtain mixed solution, transferring the obtained mixed solution into a reaction kettle, reacting for 12h at 180 ℃ to obtain viscous colloid, freeze-drying the viscous colloid to obtain precursor powder, calcining the precursor powder for 6h at 650 ℃ under argon atmosphere to obtain Na with irregular sheet structure4Fe0.5Mn0.5V(PO4)3A positive electrode material of a sodium ion battery. It is a trigonal system with a space group of R-3c and a uniform phase.
Na prepared in this example4Fe0.5Mn0.5V(PO4)3Button type electricity assembled by positive electrode material of sodium ion battery and sodium sheetAnd the button cell has a specific discharge capacity of 76.3mAh/g at a rate of 5C.
Comparative example 1:
0.04mol of sodium acetate, 0.003mol of ferrous oxalate, 0.007mol of manganese acetate, 0.01mol of ammonium metavanadate and 0.03mol of ammonium dihydrogen phosphate are dissolved in 150m L of deionized water, 60m of mixed solution of L of tetraethylene glycol and ethylene glycol (volume ratio is 1: 1) is added, stirring is carried out for 1h at room temperature to obtain mixed solution, then the obtained mixed solution is transferred into a reaction kettle, reaction is carried out for 10h at 180 ℃ to obtain viscous colloid, then the viscous colloid is frozen and dried to obtain precursor powder, the precursor powder is calcined for 8h at 750 ℃ under argon atmosphere, and the discharge specific capacity of the button cell assembled by the obtained material is only 18.6mAh/g at the rate of 5C.
Comparative example 2:
0.04mol of sodium acetate, 0.005mol of ferrous oxalate, 0.005mol of manganese acetate, 0.01mol of ammonium metavanadate and 0.03mol of ammonium dihydrogen phosphate are dissolved in 150m L deionized water, the mixture is stirred for 1h at room temperature, the obtained mixed solution is transferred to a reaction kettle, the obtained mixed solution reacts for 10h at 180 ℃ to obtain solution with precipitate, the obtained solution is freeze-dried to obtain precursor powder, the precursor powder is calcined for 8h at 750 ℃ under argon atmosphere, the obtained material has no corresponding crystal structure and is blocky, and the addition of the mixed solution of tetraethylene glycol and ethylene glycol is used for Na forming a flaky structure4Fe0.5Mn0.5V(PO4)3It is of great importance.
Comparative example 3:
taking 0.04mol of sodium acetate, 0.005mol of ferrous oxalate, 0.005mol of manganese acetate, 0.01mol of metavanadate and 0.03mol of ammonium dihydrogen phosphate into 150m L deionized water, adding 60m of mixed solution of L of tetraethylene glycol and ethylene glycol (volume ratio is 1: 4), stirring for 1h at room temperature to obtain mixed solution, transferring the obtained mixed solution into a reaction kettle, reacting for 8h at 180 ℃ to obtain viscous colloid, freeze-drying the viscous colloid to obtain precursor powder, calcining the precursor powder for 8h at 750 ℃ under argon atmosphere to obtain Na4Fe0.5Mn0.5V(PO4)3The material has no irregular sheet-like structure.
Na prepared by this comparative example4Fe0.5Mn0.5V(PO4)3The button cell is assembled by the positive electrode material of the sodium-ion battery and the sodium sheet, and tests show that the button cell has the specific discharge capacity of 41.2mAh/g under the multiplying power of 5C, and the specific discharge capacity of the button cell is greatly lower than that of Na with an irregular sheet structure4Fe0.5Mn0.5V(PO4)3A positive electrode material of a sodium ion battery. The volume ratio of the tetraethylene glycol and the ethylene glycol in the mixed solution of the tetraethylene glycol and the ethylene glycol is not 1: in the range of (0.5 to 2) (1: 4 in this comparative example), Na having a flaky structure cannot be obtained4Fe0.5Mn0.5V(PO4)3Material having electrochemical properties lower than Na having a lamellar structure4Fe0.5Mn0.5V(PO4)3A material.
Comparative example 4:
taking 0.04mol of sodium acetate, 0.005mol of ferrous oxalate, 0.005mol of manganese acetate, 0.01mol of metavanadate and 0.03mol of ammonium dihydrogen phosphate into 150m L deionized water, adding 60m of mixed solution of L of tetraethylene glycol and glycol (volume ratio is 1: 0.3), stirring for 1h at room temperature to obtain mixed solution, transferring the obtained mixed solution into a reaction kettle, reacting for 8h at 180 ℃ to obtain viscous colloid, freeze-drying the viscous colloid to obtain precursor powder, calcining the precursor powder for 8h at 750 ℃ under argon atmosphere to obtain Na4Fe0.5Mn0.5V(PO4)3The material has no irregular sheet-like structure. The volume ratio of the tetraethylene glycol and the ethylene glycol in the mixed solution of the tetraethylene glycol and the ethylene glycol is not 1: in the range of (0.5 to 2) (1: 0.3 in this comparative example), Na having a flaky structure cannot be obtained4Fe0.5Mn0.5V(PO4)3A material.
Comparative example 5:
0.04mol of sodium acetate, 0.005mol of ferrous oxalate, 0.005mol of manganese acetate, 0.01mol of ammonium metavanadate and 0.03mol of ammonium dihydrogen phosphate are taken to be put in 300m L deionized water, and addedAdding 60m of mixed solution of L tetraethylene glycol and glycol (volume ratio is 1: 1), stirring for 1h at room temperature to obtain mixed solution, transferring the mixed solution into a reaction kettle, reacting for 8h at 180 ℃ to obtain viscous colloid, freeze-drying the viscous colloid to obtain precursor powder, calcining the precursor powder for 8h at 750 ℃ under argon atmosphere to obtain Na4Fe0.5Mn0.5V(PO4)3The material has no irregular sheet-like structure.
Na prepared by this comparative example4Fe0.5Mn0.5V(PO4)3The button cell is assembled by the positive electrode material of the sodium-ion battery and the sodium sheet, and tests show that the button cell has the specific discharge capacity of 37.7mAh/g under the multiplying power of 5C, and the specific discharge capacity of the button cell is greatly lower than that of Na with an irregular sheet structure4Fe0.5Mn0.5V(PO4)3Note that when the concentration of vanadium ions in a solution formed by dissolving a sodium source, an iron source, a manganese source, a vanadium source, and a phosphorus source in a stoichiometric ratio in deionized water is less than 0.05 mol/L (this comparative example is 0.033 mol/L), Na having a lamellar structure cannot be obtained4Fe0.5Mn0.5V(PO4)3Material having electrochemical properties lower than Na having a lamellar structure4Fe0.5Mn0.5V(PO4)3A material.
Comparative example 6:
taking 0.04mol of sodium acetate, 0.005mol of ferrous oxalate, 0.005mol of manganese acetate, 0.01mol of ammonium metavanadate and 0.03mol of ammonium dihydrogen phosphate into 70m L deionized water, adding 60m of mixed solution of L of tetraethylene glycol and glycol (volume ratio is 1: 1), stirring for 1h at room temperature to obtain mixed solution, transferring the obtained mixed solution into a reaction kettle, reacting for 8h at 180 ℃ to obtain viscous colloid, freeze-drying the viscous colloid to obtain precursor powder, calcining the precursor powder for 8h at 750 ℃ under argon atmosphere to obtain Na4Fe0.5Mn0.5V(PO4)3The material has no irregular sheet-like structure. Illustrating vanadium ions in a solution formed when a sodium source, an iron source, a manganese source, a vanadium source and a phosphorus source are dissolved in deionized water in a stoichiometric ratioAt a concentration of more than 0.1 mol/L (0.14 mol/L in this comparative example), Na having a flaky structure cannot be obtained4Fe0.5Mn0.5V(PO4)3A material.
Comparative example 7:
taking 0.04mol of sodium acetate, 0.005mol of ferrous oxalate, 0.005mol of manganese acetate, 0.01mol of ammonium metavanadate and 0.03mol of ammonium dihydrogen phosphate into 150m L of deionized water, adding 60m of mixed solution of L of tetraethylene glycol and glycol (volume ratio is 1: 1), stirring for 1h at room temperature to obtain mixed solution, transferring the obtained mixed solution into a reaction kettle, reacting for 16h at 180 ℃ to obtain viscous colloid, freeze-drying the viscous colloid to obtain precursor powder, calcining the precursor powder for 8h at 750 ℃ under argon atmosphere to obtain Na4Fe0.5Mn0.5V(PO4)3The material has no irregular sheet-like structure. The reaction time of the mixed solution in the reaction kettle is not in the range of 8 h-12 h (16 h in the comparative example), and Na with irregular sheet structure cannot be obtained4Fe0.5Mn0.5V(PO4)3A material.
Comparative example 8:
taking 0.04mol of sodium acetate, 0.005mol of ferrous oxalate, 0.005mol of manganese acetate, 0.01mol of ammonium metavanadate and 0.03mol of ammonium dihydrogen phosphate into 150m L of deionized water, adding 60m of mixed solution of L of tetraethylene glycol and glycol (volume ratio is 1: 1), stirring for 1h at room temperature to obtain mixed solution, transferring the obtained mixed solution into a reaction kettle, reacting for 6h at 180 ℃ to obtain viscous colloid, freeze-drying the viscous colloid to obtain precursor powder, calcining the precursor powder for 8h at 750 ℃ under argon atmosphere to obtain Na4Fe0.5Mn0.5V(PO4)3The material has no irregular sheet-like structure. The reaction time of the mixed solution in the reaction kettle is not in the range of 8 h-12 h (6 h in the comparative example), and Na with irregular sheet structure cannot be obtained4Fe0.5Mn0.5V(PO4)3A material.
Comparative example 9:
taking 0.04mol of sodium acetate, 0.005mol of ferrous oxalate, 0.005mol of manganese acetate and 0.01mol of metavanadiumAdding ammonium phosphate and 0.03mol of ammonium dihydrogen phosphate into 150m L deionized water, adding 60m L of mixed solution of tetraethylene glycol and ethylene glycol (volume ratio is 1: 1), stirring at room temperature for 1h to obtain mixed solution, transferring the mixed solution into a reaction kettle, reacting at 180 ℃ for 10h to obtain viscous colloid, freeze-drying the viscous colloid to obtain precursor powder, calcining the precursor powder at 550 ℃ under argon atmosphere for 8h, wherein XRD of the product does not have the corresponding peak shape of a target product, and when the calcining temperature is not within the range of 650-850 ℃ (550 ℃ in the comparative example), Na cannot be obtained4Fe0.5Mn0.5V(PO4)3Target products of formula (I).
Comparative example 10:
taking 0.04mol of sodium acetate, 0.005mol of ferrous oxalate, 0.005mol of manganese acetate and 0.01mol of metavanadate and 0.03mol of ammonium dihydrogen phosphate into 150m L of deionized water, adding 60m of mixed solution of L of tetraethylene glycol and glycol (volume ratio is 1: 1), stirring for 1h at room temperature to obtain mixed solution, transferring the obtained mixed solution into a reaction kettle, reacting for 10h at 180 ℃ to obtain viscous colloid, freeze-drying the viscous colloid to obtain precursor powder, calcining the precursor powder for 16h at 900 ℃ under argon atmosphere, wherein XRD of the product does not have the corresponding peak shape of a target product, and when the calcining temperature is not in the range of 650-850 ℃ and the calcining time is not in the range of 6 h-12 h (900 ℃ and 16h in the comparative example), Na cannot be obtained4Fe0.5Mn0.5V(PO4)3Target products of formula (I).
Claims (9)
1. The positive electrode material of the sodium-ion battery is characterized in that the molecular formula of the positive electrode material of the sodium-ion battery is Na4Fe0.5Mn0.5V(PO4)3It is a trigonal system, R-3c space group, sheet structure.
2. The positive electrode material for sodium-ion batteries according to claim 1, wherein the specific surface area of the positive electrode material for sodium-ion batteries is 3-100 m2/g。
3. A method for preparing a positive electrode material for a sodium-ion battery according to claim 1 or 2, comprising the steps of:
(1) dissolving a sodium source, an iron source, a manganese source, a vanadium source and a phosphorus source in deionized water according to a stoichiometric ratio, enabling the concentration of vanadium ions in the solution to be 0.05-0.1 mol/L, then adding a mixed solution of tetraethylene glycol and ethylene glycol, and stirring at room temperature to obtain a mixed solution, wherein the volume ratio of the tetraethylene glycol to the ethylene glycol in the mixed solution of the tetraethylene glycol and the ethylene glycol is 1 (0.5-2);
(2) transferring the mixed solution obtained in the step (1) into a reaction kettle, reacting for 8-12 h at 160-200 ℃ to obtain viscous colloid, and then freeze-drying the viscous colloid to obtain precursor powder;
(3) and (3) calcining the precursor powder obtained in the step (2) for 6-12 hours at the temperature of 650-850 ℃ in an inert atmosphere to obtain the positive electrode material of the sodium-ion battery.
4. The method for preparing the positive electrode material for the sodium-ion battery according to claim 3, wherein in the step (1), the ratio of the volume of the mixed solution of the tetraethylene glycol and the ethylene glycol to the volume of the deionized water is 1: (1.5-3.5).
5. The method for preparing the positive electrode material of the sodium-ion battery according to claim 3, wherein in the step (1), the stirring time at room temperature is 0.5-1.5 h.
6. The method for preparing the positive electrode material for the sodium-ion battery according to claim 3, wherein in the step (1), the sodium source is one or more of sodium acetate, sodium carbonate, sodium bicarbonate, sodium dihydrogen phosphate and disodium hydrogen phosphate; the iron source is one or more of ferrous oxalate, ferrous acetate, ferric citrate and ferric ammonium citrate.
7. The method for preparing the positive electrode material of the sodium-ion battery according to claim 3, wherein in the step (1), the manganese source is one or more of manganese acetate, manganese oxalate and manganese nitrate; the vanadium source is one or more of metavanadate, vanadium acetylacetonate, vanadyl acetylacetonate and sodium orthovanadate; the phosphorus source is one or more of phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate, disodium hydrogen phosphate and sodium dihydrogen phosphate.
8. The method for preparing the positive electrode material of the sodium-ion battery according to claim 3, wherein in the step (3), the inert atmosphere is one or more of argon gas, nitrogen gas and hydrogen-argon gas mixture.
9. A sodium-ion battery, characterized in that the sodium-ion battery positive electrode material according to claim 1 or 2 or the sodium-ion battery positive electrode material prepared by the preparation method according to any one of claims 3 to 8 is used in the sodium-ion battery.
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| CN114142026B (en) * | 2021-12-02 | 2023-10-20 | 河南师范大学 | Manganese-based polyanion positive electrode material, preparation method thereof and sodium ion battery |
| CN115084502A (en) * | 2022-05-13 | 2022-09-20 | 福州大学 | NASICON type structure ternary sodium ion battery positive electrode material, preparation method and application thereof |
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